Sintered bodies based on niobium suboxide

ABSTRACT

Disclosed are sintered bodies that include: (a) 30 to 100 mol % of NbO x , wherein 0.5&lt;x&lt;1.5; and (b) 0 to 70 mol % of MgO. The sintered bodies may be used as inert apparatuses in the production of niobium suboxide powder or niobium suboxide anodes, or as chemically resistant components in chemical apparatuses.

CROSS REFERENCE TO RELATED PATENT APPLICATION

The present patent application claims the right of priority under 35U.S.C. §119 (a)-(d) of German Patent Application No. 103 47 702.0, filedOct. 14, 2003.

FIELD OF THE INVENTION

The present invention relates to a sintered body based on niobiumsuboxide. In particular, the present invention relates to sinteredshaped bodies which, on account of their resistance to chemicals, areused in chemical apparatus and preferably for the production of anodesfor solid electrolyte capacitors, in particular sintered anodes madefrom niobium suboxide.

BACKGROUND OF THE INVENTION

Anodes of this type are produced by sintering fine niobium suboxideparticles to form a sponge-like structure with an extremely largesurface area. A dielectric niobium pentoxide layer is produced on thissurface by electrolytic oxidation, and the capacitor cathode, which mayconsist of manganese dioxide or a polymer electrolyte, is produced onthe pentoxide layer. The process used to produce anodes or capacitors ofthis type, as well as the production of the capacitor precursor powders,includes a range of mechanical and thermal treatment steps in vacuo orreactive and/or protective gas, which entail the risk of contaminationwith elements which have an adverse effect on the capacitor properties.Therefore, according to WO 021086923 A2, it is proposed that allequipment used for the mechanical or thermal treatment involved in theproduction of anodes consist of niobium metal or at least be coated withniobium metal.

One drawback in this context is that niobium metal is a so-called oxygengetter material, which tends to take up oxygen at high temperatures.Accordingly, during high-temperature treatment steps involved in theproduction of niobium suboxide anodes, which may involve temperatures ofup to 1600° C., there is a high risk of oxygen being withdrawn from theniobium suboxide in an uncontrolled way, in particular if there isdirect contact between the niobium suboxide and the niobium metal atthis high temperature. Furthermore, the niobium metal becomesincreasingly brittle as a result of the uptake of oxygen when usedrepeatedly, and therefore typically has a short service life.

SUMMARY OF THE INVENTION

According to the invention, it is now proposed that devices which areused in the production of anodes of this type be formed as sinteredbodies based on niobium suboxide and if appropriate magnesium oxide.

Examples of devices of this type include vessels, reactor vessels,reactor linings, mill linings, milling beads, milling rollers, pressmoulds, press rams, etc.

In accordance with the present invention, there is provided a sinteredbody comprising:

-   -   (a) 30 to 100 mol % of NbO_(x),        -   wherein x is greater than 0.5 and less than 1.5 (i.e.,            0.5<x<1.5); and    -   (b) 0 to 70 mol % of MgO,        the mole percents being based in each case on the total moles of        NbO_(x) and MgO.

The invention also provides a method for producing solid electrolytecapacitors comprising a niobium suboxide anode, said method comprising:

pre-treating a pre-cursor of said niobium suboxide anode by a treatmentmeans selected from the group consisting of mechanical treatment,thermal treatment and combinations thereof,wherein said pre-treatment is performed in an apparatus comprising atleast one sintered body according to the present invention upon whichsaid pre-cursor of said niobium suboxide anode is placed.

In a further embodiment of the above method, said method furthercomprises the steps of

providing a sinter plate comprising said sintered body according to thepresent invention,placing said pre-cursor of said niobium suboxide anode on said sinterplate,pre-treating said precursor of said niobium suboxide.

In general, said pre-cursor of a niobium suboxide anode is produced bypressing.

The sintered bodies according to the present invention are particularlysuitable for use in chemical apparatuses, thus the present inventionalso provides a chemical apparatus comprising chemically resistantcomponents fabricated from the sintered body according to the presentinvention.

Such a chemical apparatus is particularly suitable for the production ofcapacitor grade niobium suboxide powder.

Unless otherwise indicated, alt numbers or expressions, such as thoseexpressing quantities of ingredients, mole and volume percents, processconditions, etc., used in the specification and claims are understood asmodified in all instances by the term “about.”

DETAILED DESCRIPTION OF THE INVENTION

The sintered bodies preferably contain niobium suboxide of the formulaNbO_(x), where 0.7<x<1.3.

It is particularly preferable for the sum of the molar percentages ofniobium suboxide and magnesium oxide to be 100% with the exception ofinevitable foreign element impurities. In particular, the sinteredbodies should be substantially free of iron, chromium, nickel, alkalimetals and halogens. The iron, nickel, chromium, sodium, potassium,chlorine and fluorine impurities should particularly preferably eachamount to less than 10 ppm, particularly preferably less than 5 ppm, andalso preferably in total less than 30 ppm. On the other hand, impuritiesor alloying elements of vanadium, tantalum, molybdenum and tungstenamounting to up to a few mol %, for example up to 5 mol %, are harmless.

The sintered bodies according to the invention may advantageouslyconsist of 35 to 100 Mol % of NbO_(x) and 65 to 0 Mol % of MgO. Thesintered bodies according to the invention preferably consist of 30 to60 Mol % of NbO_(x), and 70 to 40 Mol % of MgO, particularly preferablyof 45 to 60 Mol % of NbO_(x) and 55 to 40 Mol % of MgO.

Preferred sintered bodies according to the invention have porosities ofless than 30% by volume, more specifically the sintered bodies accordingto the invention have porosities of from greater than 0% by volume toless than 30%, particularly preferably less than 20% by volume, morespecifically the sintered bodies according to the invention haveporosities of from about 1% by volume to less than 15% by volume. Thepercent volumes being based on the total volume of the sintered body.

The sintered bodies containing magnesium oxide in accordance with theinvention preferably comprise microstructures which includesubstantially homogeneous niobium suboxide-rich regions and magnesiumoxide-rich regions which each extend at most 1.5 μm, preferably at most1.0 μm in at least one direction. It is preferable for the niobiumsuboxide-rich regions to comprise at least 95%, particularly preferablyat least 99%, of niobium suboxide. The magnesium oxide-rich regionspreferably comprise up to 99% of magnesium oxide.

The sintered bodies according to the invention can be produced usingstandard ceramic processes. For example, the shaping can be performed byaxial and/or isostatic pressing, extrusion, conventional pressure-freeor pressurized slip casting or also by injection moulding. Depending onthe process used, suitable organic auxiliaries, such as for example PVA,PEG, etc. (for pressing), wax or plasticizers which are commerciallyavailable for this purpose (for the injection moulding, etc.), whichafter moulding can be expelled (binder removal) without leaving anyresidues by means of a heat treatment in air, under protective gas or invacuo without altering the basic properties of the inorganic basepowder, are added to the powder in a manner which is known per se fromsintering technology. In air, a temperature of 250° C., preferably 150°C., should not be exceeded, in order to prevent oxidation of the niobiumsuboxide.

In the case of shaping by pressing, the addition of the organicauxiliaries may advantageously be combined with a granulation step inorder to improve the flow properties of the powder.

In the case of slip casting, preliminary drying, preferably in air, hasto be carried out after demoulding and prior to the binder removal.Furthermore, a (careful) mechanical treatment using chip-formingprocesses, such as turning, milling, drilling, etc., can be carried outafter the shaping step and prior to the binder removal, in order to makethe bodies as close as possible to the desired net shape of the sinteredbody. A treatment of this type may also be carried out after the binderremoval and any pre-sintering step for consolidating the shaped body, inwhich case machining processes such as dry or wet grinding may also beused.

The sintering itself is carried out in gastight furnaces under aprotective gas atmosphere, such as argon or gas mixtures based on argontogether with typically 3 to 10% by volume of hydrogen or the like inorder to counteract a change in the oxidation state of the niobiumsuboxide. Before the sintering begins, the furnace is purged with theprotective gas or evacuated and flooded with the protective gas. Toavoid direct contact between the shaped body to be sintered and thefurnace lining, the shaped body is mounted on supports/spacers (“firingaids”) made from materials which are thermally and chemically stable atthe sintering temperature and do not enter into any reaction with thesuboxide. Sintering aids made from dense or porous silicon carbide haveproven particularly suitable. The sintering preferably takes place attemperatures of less than 1700° C., particularly preferably between 1550and 1650° C., with a slow heating rate of less than 10 K/min to thesintering temperature, preferably 1 to 3 K/min in the upper temperaturerange from 1100° C. up to the sintering temperature, with a holding timeat the sintering temperature of preferably less than 10 hours, dependingon the desired densification of the shaped body and the particle size ofthe niobium suboxide and optionally magnesium oxide powders used.

The starting material used for the production of the sintered bodiesaccording to the invention is preferably commercially availablehigh-purity niobium pentoxide with a specific surface area of from 5 to20 m²/g. The niobium pentoxide, either as such or after reduction inflowing hydrogen to form the niobium dioxide, can be reduced to thesuboxide by means of magnesium vapour at a temperature of from 950 to1150° C. This forms an agglomerate powder which contains magnesium oxideinclusions.

This powder can be used as such after milling to produce the sinteredbodies according to the invention. If the starting point is niobiumdioxide, sintered bodies which contain approximately 50 Mol % of MgO areobtained. On the other hand, if the starting point is niobium pentoxide,sintered bodies which contain approximately 67 Mol % of magnesium oxideare obtained.

The starting point for the production of sintered bodies which do notcontain any magnesium oxide is preferably likewise fine-particle niobiumpentoxide with a high specific surface area. This niobium pentoxide isreduced in flowing hydrogen at a temperature of from 1100 to 1400° C. toform the niobium dioxide. Some of the niobium dioxide is reduced furtherin magnesium vapour to form the niobium metal. Then, the magnesium oxidewhich is formed is washed out of the niobium metal by means of acids,for example sulphuric acid. The niobium metal is then heated with astoichiometric quantity of niobium dioxide in a hydrogen-containingatmosphere to 1100 to 1600° C., leading to conversion to the niobiumsuboxide, NbO. Other compositions of the sintering powder in accordancewith the invention are obtained by correspondingly varying thequantitative ratios of the respective reaction components or mixtures.

To attain the relatively high densities of the sintered bodies, it ispreferable to use fine-particle agglomerate powders, particularlypreferably a screened fraction below 38 μm, more preferably below 20 μm.

Furthermore, the powders which can be used in accordance with theinvention to produce the sintered bodies, are eminently suitable forproducing coatings by means of high-temperature or plasma spraying, inwhich case it is possible to produce surface layers which are similar tosintered structures on metals such as niobium, tantalum, molybdenumand/or tungsten. In this case, it is if appropriate possible toadditionally use niobium metal powder in subordinate quantities of up to20% by weight, preferably between 10 and 18% by weight, as binder.Coated devices of this type made from niobium, tantalum, molybdenum ortungsten, according to the invention, are also suitable for theproduction of solid electrolyte capacitors based on niobium suboxide.Metal devices of this type provided with a coating which is similar to asintered structure are also intended to be encompassed by the term“sintered body” in accordance with the invention.

PRODUCTION EXAMPLE

The production of a sintering plate for solid electrolyte capacitoranodes is explained below by way of example for the sintered bodiesaccording to the invention.

A niobium suboxide powder of composition NbO with a particle size ofless than 38 μm and a particle size distribution in accordance with ASTMB822 (Malvern Mastersizer) corresponding to a D10 value of 2.8 μm, a D50value of 11.4 μm and a D90 value of 25.2 μm is used. The flow propertiesof the powder are improved by screening granulation and a tumblingtreatment without further additives sufficiently for uniform filling ofa press mould to be possible. A hard metal press mould with a squareaperture with a side length of 125 mm is used. The granulated powder isintroduced into the mould and compacted at 2 kN/cm². The pressed body,with dimensions of approximately 125×125×15 mm³, after demoulding, iswelded into a plastic film and compressed further isostatically at 200Mpa. The result is a pressed body of approx. 122×122×13 mm³. Thispressed body is machined on a conventional milling machine in such a waythat a dish-like part with an encircling rim with a height of 13 mm anda wall thickness of 5 mm for both the base and the rim remains.

The green machined part is placed without further pretreatment, inside aSiC vessel, into a gastight furnace heated by means of graphiteresistance heating and is sintered. At the start of the sintering, thefurnace is evacuated and flooded with a gas mixture comprising 97% byvolume of argon and 3% by volume of hydrogen. The heating programmefollows a heat-up rate of 10 K/min up to 500° C., a heat-up rate of 5K/min up to 1100° C., then a heat-up rate of 2.5 K/min up to 1600° C., aholding time of 3 hours at 1600° C., a controlled cooling rate of 5K/min down to 800° C., followed by uncontrolled cooling to below 150° C.The shaped part which is then removed from the furnace has a density of6.9 g/cm³ and a Vickers-Hardness HV 10 of 14 Gpa. It may optionally beremachined on the inside and/or outside in order to establishpredetermined geometry and surface structures.

Although the invention has been described in detail in the foregoing forthe purpose of illustration, it is to be understood that such detail issolely for that purpose and that variations can be made therein by thoseskilled in the art without departing from the spirit and scope of theinvention except as it may be limited by the claims. The prioritydocument and all further documents cited herein are incorporated byreference for all useful purposes.

1-11. (canceled)
 12. A method for producing solid electrolyte capacitorscomprising a niobium suboxide anode, said method comprising:pre-treating a pre-cursor of said niobium suboxide anode by a treatmentmeans selected from the group consisting of mechanical treatment,thermal treatment and combinations thereof, wherein said pretreatment isperformed in an apparatus comprising at least one sintered body uponwhich said pre-cursor of said niobium suboxide anode is placed andwherein the sintered body comprises a) 30 to 100 mol % of NbO_(x),wherein 0.5<x<1.5 b) 0 to 70 mol % of MgO.
 13. The method of claim 12,further comprising providing a sinter plate comprising said sinteredbody, placing said pre-cursor of said niobium suboxide anode on saidsinter plate, pre-treating said precursor of said niobium suboxide. 14.The method of claim 12, wherein said sintered body has a porosity offrom greater than 0% by volume to less than 30% by volume.
 15. Themethod of claim 13, wherein said sintered body has a porosity of fromgreater than 0% by volume to less than 30% by volume.
 16. The method ofclaim 12, wherein said sintered body comprises: (a) 35 to 100 Mol % ofNbO_(x); and (b) 65 to 0 Mol % of MgO.
 17. The method of claim 12,wherein said sintered body comprises: (a) 45 to 60 Mol % of NbO_(x); and(b) 55 to 40 Mol % of MgO.
 18. The method of claim 15, wherein saidsintered body comprises: (a) 45 to 60 Mol % of NbO_(x); and (b) 55 to 40Mol % of MgO.
 19. The method of claim 12, wherein 0.7<x<1.3.
 20. Themethod of claim 18, wherein 0.7<x<1.3.
 21. The method of claim 14,wherein said porosity is from about 1% by volume to less than 15% byvolume.
 22. The method of claim 20, wherein said porosity is from about1% by volume to less than 15% by volume.
 23. The method of claim 12,wherein said sintered body has a microstructure comprising homogeneous,NbO_(x)-rich regions and MgO-rich regions, which each extend at most 1.5μm in at least one direction.
 24. The method of claim 23, wherein saidsintered body has a microstructure comprising homogeneous, NbO_(x)-richregions and MgO-rich regions, which each extend at most 1.5 μm in atleast one direction.